Process for making finished motor fuel



Sept. 21, 1943. MARSHALL I 23305069., PROCESS FOR MAKING FINISHED MOTOR FUEL" v Filed Oct. 28, 1939 OUTLET .-s dRUBBE --IIB HEAv y Y/Mara OUTLET T/ONA TING To W572 are RESSUPE REA c T/O/V CHAMBER COIL , HEA r/lvc a supply of hydrocarbonoil tobe converted to a finished fuel of high octane number and low acid heat and low gum content. "This hydrocarbon oil may have been derived from any source and preferably consists of hydrocarbons boiling substantially in the gasoline range, say from 100 to 450 F. The'character of the hydrocarbon 011 is immaterial, i. e.,' it may be paraflinic, naphthenic,

aromatic or olefinic and it may have either a high or low sulfur content. Hydrocarbon oil is drawn from tank I through line 2 by means of pump 3 hydrogen are heated to a temperature somewhat above the temperature to be maintained in the reaction zone. Heated oil leaves coil through line I I and heated hydrogen leaves coil I Uthrough line I2 and the twoconverge in line I3 which carries a mixture of heated oil and hydrogen into a reaction chamber I4 which contains a catalytic material l5, the nature of which will be more fully disclosed below. r

A plurality of pipes .JSextends through the walls-of the reaction zone and terminates in a series of smallopenings in the upper portion thereof. A portion of the gasrich in free hydro-. gen flowing through line 8 is diverted through, line I! into lines I6 through which the gas is admltted directly into the upper portion of the re action zone. .A plurality of valves I8 is provided in the lines I6 so that gas maybe introduced through one or more of the pipes I6. The funcreaction zone will be between 500 and 3000 cubic feet per barrel of .oil.

'ating and stabilizing means 23.

Products of reaction leave reaction zone I4 through line I9, pass through a cooling means 20 and thence discharge into a high pressure separator 2| wherein gaseous and liquid products'may be separated. Liquid products are removed from high pressure separator 2i through line 22 and introduced directly into a fraction Constituents which are too volatile for the desired product are removed from the fractionating means through line and may be passed to a gas absorption system or otherwise disposed of. Constituents which are too high boiling for the desired prodnot, such as heavy polymer fractions, are removed from'theiractionating means 23 through line 25, The desired product is removed from the fractionating means 23 through'line 28 and collected in a storage tank 21. Ordinarily it will be found that this product does not require the usual acid or clay treatment because the acid heat and gum content will be sufiiciently low to meet most specifications. However, it may be desirable or necessaryto rerun the product to a'specifi'edend point;

' 'Retuming to the hig'h pressure separator 2|,

' gaseous pr'oducts are removed therefrom through line*28.- 'They" then pass througha booster 2B which recompresses themto reaction pressureor above and returns them through line 30 to the tion of the gas rich in free hydrogen introduced into the upper portion of the reaction zone is twofold, namely, it'serves to increase the partial pressure of the hydrogen in the reacting materials at the point of. introduction and it also serves simultaneously to cool the reacting materials to a temperature at which a hydrogenating effect predominates.

The middle and lower portions of the reaction zone are maintained at a temperature between 850 and 1050 F., preferably between 900 and 1000 F., and the upper portion is maintained by means of the introduction of cold hydrogen-containing gas at a substantially lower temperature, say between 600 and 850 F. The pressure in the reaction zone is maintained between about and 500 pounds per square inch, preferably be- .tween 50 and 300 pounds per square inch. The oil is fed to the reaction zone at a rate between 0.1 and 4.0 volumes of liquid oil per volume of catalyst per hour, preferably between 0.2 and 1.5 v./v./hr. The quantity of gas introduced with the oil through line I3 into the bottom portion of the tower is between 1000 and 3000 cubicfeet per barrel of oil and this gas should contain between 20 and 90 mol percent of free hydrogen, preferably between 40 and 70 mol percent. The quantity of gas introduced into the upper portion of the reaction zone through the plurality of lines I6 will be adjusted according to the temperature of the entering gas. the temperature to which it is desired to cool the reacting materials in the upper portion offthe reaction zone and the proportion of the upper part of the reaction zone which it is desired to maintain under predominantly hydrogenating conditions. In

general, it may be said that the quantity of gas hydrogen holder 6 from which they maybe recycled continuously through the reaction zone. In theevent that it isdesired to increase the hydrogen concentration in the' recycle gases this may be accomplished bypassing a portion or all of the gases leaving the high pressure separator 2! through a scrubbing means designated by the numeral 3| prior to their return to the hydrogen holder 6. The purpose of the scrubbing means is to remove a substantial proportion of the hydrocarbon constituents from the recycle gases. This may be done by any suitable means, such as by scrubbing the recycle gases with a light hydrocarbon oil which will absorb hydrocarbons but substantially no hydrogen.

In the operation of the process the flow of oil through the reaction zone I 4 is continued until (1) there ceases to be an overall net production of free hydrogen, or (2) the activity of the catalyst falls to such an extent that the octane number of the product produced falls substantially below a predetermined level, whichever of these two things occurs first, In most cases it will be found that the second of these things will occur first. When this happens the flow of oil through the reaction zone is stopped and the catalyst is t then subjected in'situ to a regeneration treatair with the inert gas.

This will ordinarily indicate that no more carbonaceous material capable of being burned off remains on the catalyst. For purposes of regeneration inert gases, such as flue gases, carbon dioxide, nitrogen and the like may be used. The oxygen is conveniently supplied by mixing The quantity of oxygen in the regenerating gases will rangebetween 0.1

and gases are i The temperature at which the hot introduced into the -.reaction zone should be between about i V i should be taken that the maximum temperature developed in the reaction zone does not rise ep- 600 and'95flf F. and care assopee o! aluminar-y t itiieac ive metal-pr d im a preciably above 1200 to 130051. because'temperatures higher than this appear adversely toaffect the structure of the catalyst, Temperature may be controlled by regulating the percentage of oxygen in the hot gases. Regeneration under pressure" between 50 and 200 pounds per square inch is advantageous because it is found that the ignition temperature and thetime required for regeneration may be reduced. Following regeneration the flow of oil through the reaction zone may be resumed and the alternation of re action and regeneration cycles may be continued for an indefinite period of time until thecat alyst requires replacement,

The length of a reaction cycle will ordinarily be between 6 and 12 hours or more and the length same or substantially shorter. Although only one reaction zone has been illustrated in the drawing, it will be understood that two or morereaction zones may be hooked up to the same system so that while one reaction zone is on a regeneration cycle another reaction zone may be on a reaction cycle.

When'starting up the process, hydrogen or a gas rich in free hydrogen may have tobe supplied from an extraneous source. However, after ,once having started up, the process is operated V under such conditions that there is a net production of free hydrogen therein so that it is not of time required for regeneration may be the solution. containing soluble;

. we t-11 11 49 and he a other; metal or. metals. '1 The, catalyst catalytic material or. it, may [be provided with two or more shelves-or trays on each of which a bed oicatalyst' be supported.

'In'the early stag i a reactionxcycle. the catalyst will be 'moreactive in promoting dehydrogenation andaromatization than in the later ,used' invarious shapesi and'iormsfluch i jas pills, tablets, granules or'other pieces oi regular. or irregular shape. The .entire react o zone may" be-fllle'd with smalljpieces of stages. Asthe reaction;cyclefproceeds, it is desirable to increase progressively the portion of the reaction zone which ji s maintained under conditions which favor dehydrogenation and aromatlzation in order to ,oilset'j the decrease injcatralytic activi-tyiand tol maintain I a substantially tration, it'may' besaidthat at the beginning of a reaction cycle' it may only be necessaryflto devote approximately one-dial! 'of' the reaction zone to dehydrogenation and aromatization, while as the reaction proceeds more and more of the reaction zone is devoted'to dehydrogenationuntil finally near the end of a reaction cycle approximately two-thirds'or more of the entire renecessary'to add hydrogen from an extraneous source because the hydrogen initially added and that produced in the process may be continuously recycled. Even if hydrogen is not available from an extraneous source for starting up, it may be readily produced by operating the process for a period of several hours or more at atmospheric or slightly higher pressure. 'Under these condiaction zone may be maintained under dehydrogenating conditions. This, of course, means that The progressive increase in the size of the portion oi the reaction zone devoted to dehydrogenation may beconvenientlyeflecited by adjusting the point or points at which the cold hydrogen-contaming gas is introduced into the-upper portion of the reaction zone. For example, at the tions substantial quantities of hydrogen are produced and after relatively short periods oi operation sufilcient hydrogen will have been produced to enable the process to proceed under the desired conditions. The pressure can be gradually in-' ,creased to the desired level for reaction without interrupting operation.

The catalysts used may be selected from a wide 1 variety of different materials which promote reforming. Preferred catalysts are compounds such as the oxides or sulfides of metals of the IV, V, VI and VIII groups of the periodic system. These may be used alone, in various mixtures or combinations' with each otherjor in combination with may be prepared by mechanical mixing of the various ingredients, by impregnating the carrier or support with a solution of the active metal compound and then heating the impregnated start the cold gas may be introduced through the lowermost of the plurality of pipes 10 so that a relatively large section of the upper portion of the reaction zone is maintained under predominantly hydrogenating conditions. As it is necessary to increase the portion devoted to dehydrogenation, the point at which the cold gas is introd'u'ced may be progressively raised so that finally near the end" or the reaction'cycle the cold hydrogen-containing gas will be introduced almost entirely through the uppermost of the pipes l6. Notwithstanding that the portion of the reaction zone devoted to hydrogenation is thus progressively decreased, the degree of hydrogenation obtained can be maintained substantially constant by progressively increasing the temperature at which the upper portion or the reaction zone is maintained. In the drawing f the feed has been shown as being introduced into mass to convert the metal compound to the oxide,

or by co-precipitating the'carrier, as in the case the bottom portion of the reaction zone and the the portion of the reaction zone devoted to hy- Q drogenation will progressively decrease.

products are removed 'from the upper portion thereof. It will be understood, however, that the now may be reversed with equally satisfactory results so-that theieed enters the top and the. products-are withdrawn from the bottom.

With most naphthas it will be found that'the net quantity of freehydrogen produced in the dehydrogenating and aromatizing reaction will be more than sufficient to maintain the required hydrogen concentration in the recycle gasesl For example, by adjusting the operating conditions the net quantity of free hydrogen produced may range between and 500 cubic feet per barrel oi naphtha. The entire process may therefore be operated under conditions such that the hydrogen produced in thedehydrogenation section 01 the reaction zone will more than compensatefor the hydrogen which may be consumed in the hydrogenating section of the'reactlon zone with the result that there-is either no net consumption of free hydrogen or there is an overall net production of free hydrogen.

This invention is not limited by any theories of the mechanism of the reactions nor by any details which'have been given merely for pure poses of illustration but is limited only in and by the following claims in which it is intended to claim all novelty inherent in the invention.

I claim:

1. An improved process for preparing a finished internal combustion engine fuel of high octane number, low acid heat and low gum content which comprises introducing a mixture of gas rich in free hydrogen and a yaporized'hydrocarbon oil boiling substantially between 100 and 500 F.

- into a reaction zone containing a rigidly arranged catalyst which promotes reforming and is capable of being regenerated, maintaining the entire reaction zone undera total pressure between 50 and 300 pounds per square inch, maintaining that portion of the reaction zone nearest the point of introduction of the oil and gas thereinto under a partial pressure of hydrogen inthe lower range of partial pressures suitable for reforming, maintaining the remaining portion of the reaction zone at e. temperature between 600 and 850 F. and at a partial pressure of hydrogen in the upper range of partial pressures suitv able for reforming by the introduction directly at a temperature between 900 and 1000" F. and

into said remaining portion of a cold gas containing free hydrogen, progressively increasing the proportion of the entire reaction zone which is maintained at the higher temperature as the reaction cycle proceeds by progressively moving the point at which the cold gas containing the free hydrogen is introduced nearer to the exit end of the reaction zone, removing reaction products from the reaction zone, and recovering from said products a fraction boiling in the range of an intemal combustion engine fuel.

2. Process according to claim 1 in which the temperature maintained in that portion of the zone nearest the exit end of the products is v progressively increased between 600 and 850 F.'

as the proportion of the entire reaction zone which is maintained at temperatures between these limits is progressively decreased.

- EDWARD T. MARSHALL. 

